EP0605392B1 - Process for producing methoxyminoacetamide compounds - Google Patents

Process for producing methoxyminoacetamide compounds Download PDF

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EP0605392B1
EP0605392B1 EP94101360A EP94101360A EP0605392B1 EP 0605392 B1 EP0605392 B1 EP 0605392B1 EP 94101360 A EP94101360 A EP 94101360A EP 94101360 A EP94101360 A EP 94101360A EP 0605392 B1 EP0605392 B1 EP 0605392B1
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compound
formula
sub
compounds
isomer
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French (fr)
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EP0605392A1 (en
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Akira Takase
Hiroyuki Kai
Kuniyoshi Nishida
Masahiko Nagai
Shoji Shinomoto
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Shionogi and Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms

Definitions

  • the present invention relates to a process for producing methoxyiminoacetamide compounds of the formula: wherein X is hydrogen, lower alkyl, lower alkoxy or halogen; and ⁇ is any configuration of E-isomer, Z-isomer or a mixture thereof, which are useful as agricultural fungicides, and intermediates for use in the production of the compounds of the formula [I].
  • the compounds of the formula [I] are compounds which have been disclosed for the first time in EP-A-398 692 in the name of the present assignee, and they are considered to be remarkably useful compounds as agricultural fungicides having excellent fungicidal activities against microorganisms such as Piricularia oryzae , Pellicularia sasakii , Pseudoperonospora cubensis and the like.
  • the compounds of the formula [I] are produced by several routes.
  • the present inventors have found other novel synthetic routes for producing the compounds of the formula [I] which are more economical with minimum by-products.
  • the present invention provides a novel process for producing the methoxyiminoacetamide compounds of the formula [I] which are useful for agricultural fungicides.
  • the invention provides a fungicidal composition
  • a fungicidal composition comprising at least one compound of the formula [I] when produced by the process of the invention together with one or more diluents, excipients or carriers, as well as a method for controlling phytopathogenic fungi which comprises applying as an active ingredient at least one compound of formula [I] when produced by a process of the invention to a locus where phytopathogenic fungi may propagate or are propagating.
  • examples of alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms are for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
  • alkoxy having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms are for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and t-butoxy.
  • Examples of "halogen” include fluorine, chlorine, bromine and iodine.
  • Examples of the C 1 -C 6 alkyl represented by R include the same groups as those described with respect to the above X.
  • Examples of the alkali metal include potassium and sodium.
  • Examples of "halogen" represented by L include the same halogen atoms as those described with respect to the above X.
  • reaction of [V] with the compound [IV] is conducted in a solvent in the presence of a base at -20 to 120°C for 15 minutes to 5 hours.
  • the invention also includes a process for making a fungicidal composition especially for treating micro-organisms such as Piricularia oryzae, Pellicularia sasakii and Pseudoperonospora cubensis wherein a compound of formula [I] is prepared by a process in accordance with this present invention and thereafter the resulting compound is formulated into a fungicidal composition by admixing therewith one or more diluents, excipients or carriers.
  • a process for making a fungicidal composition especially for treating micro-organisms such as Piricularia oryzae, Pellicularia sasakii and Pseudoperonospora cubensis wherein a compound of formula [I] is prepared by a process in accordance with this present invention and thereafter the resulting compound is formulated into a fungicidal composition by admixing therewith one or more diluents, excipients or carriers.
  • the compound [I] is directly obtained by methylating the compound of the formula [V] with the compound [IV]. This methylation can be conducted according to the manner described below and the compound of the formula [I] can be obtained in a good yield without purification such as that by column chromatography.
  • the methylation can be conducted in a solvent such as dimethylformamide, dimethylsulfoxide, benzene, toluene, acetone, tetrahydrofuran or a mixed solvent thereof at -20 to 120°C for 15 minutes to 5 hours in the presence of a base such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium t-butoxide, sodium methylate, sodium ethylate or the like.
  • a solvent such as dimethylformamide, dimethylsulfoxide, benzene, toluene, acetone, tetrahydrofuran or a mixed solvent thereof at -20 to 120°C for 15 minutes to 5 hours in the presence of a base such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium t-butoxide, sodium methylate, sodium ethylate or the like.
  • the compound of the formula [I] thus obtained wherein X is hydrogen can be converted into a corresponding compound of the formula [I] wherein X is lower alkyl or halogen by a known method such as alkylation or halogenation.
  • the compound of formula [I] is present as E-isomer or Z-isomer, or a mixture thereof.
  • the compound of the formula [I] thus obtained can be purified, if necessary, according to a conventional method, for example, column chromatography and can be used as an agricultural fungicide according to a known method.
  • EP-B-0 468 775 Reference may be made to the parent of this application, EP-B-0 468 775 and to the co-pending divisonal application, EP-A-0 606 924 for information on procedural chemistry relevant to the present process.
  • E-2-hydroxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide (1.00 g, 0.0035 mole) was dissolved in dried acetone (7 ml), and potassium carbonate (0.63 g, 0.0046 mole) and dimethylsulfate (0.53 g, 0.0042 mole) were added to the mixture, which was reacted at room temperature for 22 hours. After completion of the reaction, water was added to the reaction mixture, which was extracted twice with methylene chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • E- ⁇ -hydroxyimino-2-(4-methylphenoxy)phenylacetic acid methyl ester (1.00 g, 0.0035 mole) was dissolved in methanol (7 ml) and 40% methylamine solution in methanol (0.54 g, 0.007 mole) was added to the mixture, which was refluxed for 70 minutes. A 40% methylamine solution in methanol (1.36 g, 0.0175 mole) was further added to the mixture, which was refluxed for 3 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to give E-2-hydroxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide (1.00 g, yield: 100.0 %) as an amorphous.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cephalosporin Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyrrole Compounds (AREA)

Abstract

A process for producing a E-isomer of the formula:wherein X is hydrogen, C<sub>1</sub>-C<sub>6</sub> alkyl, C<sub>1</sub>-C<sub>6</sub> alkoxy or halogen; A is -CONHCH<sub>3</sub> or -COOR; and R is C<sub>1</sub>-C<sub>6</sub> alkyl comprises reacting a Z-isomer of the formula [VI]:wherein X, A and R are as defined above, with an acid in a C<sub>1</sub>-C<sub>6</sub> alcohol.

Description

  • The present invention relates to a process for producing methoxyiminoacetamide compounds of the formula:
    Figure imgb0001
     wherein X is hydrogen, lower alkyl, lower alkoxy or halogen; and ∼ is any configuration of E-isomer, Z-isomer or a mixture thereof, which are useful as agricultural fungicides, and intermediates for use in the production of the compounds of the formula [I].
  • The compounds of the formula [I] are compounds which have been disclosed for the first time in EP-A-398 692 in the name of the present assignee, and they are considered to be remarkably useful compounds as agricultural fungicides having excellent fungicidal activities against microorganisms such as Piricularia oryzae, Pellicularia sasakii, Pseudoperonospora cubensis and the like.
  • In the above application, the compounds of the formula [I] are produced by several routes. However, at this time, the present inventors have found other novel synthetic routes for producing the compounds of the formula [I] which are more economical with minimum by-products.
  • The present invention provides a novel process for producing the methoxyiminoacetamide compounds of the formula [I] which are useful for agricultural fungicides.
  • In other aspects the invention provides a fungicidal composition comprising at least one compound of the formula [I] when produced by the process of the invention together with one or more diluents, excipients or carriers, as well as a method for controlling phytopathogenic fungi which comprises applying as an active ingredient at least one compound of formula [I] when produced by a process of the invention to a locus where phytopathogenic fungi may propagate or are propagating.
  • According to the present invention there is provided a process for producing a compound of the formula [I]:
    Figure imgb0002
     wherein X is hydrogen, C1-C6 alkyl,C1-C6 alkoxy or halogen; and ∼ is any configuration of E-isomer, Z-isomer or a mixture thereof, which comprises reacting a compound of the formula [V]:
    Figure imgb0003
     wherein X and ∼ are as defined above and M is hydrogen or an alkali metal, with a compound of the formula [IV}:

            CH3-L     [IV]

    wherein L is halogen or -OSO2OCH3.
  • In each compound disclosed in the present specification, examples of alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, are for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl. Examples of alkoxy having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, are for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and t-butoxy. Examples of "halogen" include fluorine, chlorine, bromine and iodine. Examples of the C1-C6 alkyl represented by R include the same groups as those described with respect to the above X. Examples of the alkali metal include potassium and sodium. Examples of "halogen" represented by L include the same halogen atoms as those described with respect to the above X.
  • Preferably the reaction of [V] with the compound [IV] is conducted in a solvent in the presence of a base at -20 to 120°C for 15 minutes to 5 hours.
  • Of the C1-C4 alkyl groups which may be present in the compound of formula [I] methyl is preferred.
  • The invention also includes a process for making a fungicidal composition especially for treating micro-organisms such as Piricularia oryzae, Pellicularia sasakii and Pseudoperonospora cubensis wherein a compound of formula [I] is prepared by a process in accordance with this present invention and thereafter the resulting compound is formulated into a fungicidal composition by admixing therewith one or more diluents, excipients or carriers.
  • The compound [I] is directly obtained by methylating the compound of the formula [V] with the compound [IV]. This methylation can be conducted according to the manner described below and the compound of the formula [I] can be obtained in a good yield without purification such as that by column chromatography.
  • For example, the methylation can be conducted in a solvent such as dimethylformamide, dimethylsulfoxide, benzene, toluene, acetone, tetrahydrofuran or a mixed solvent thereof at -20 to 120°C for 15 minutes to 5 hours in the presence of a base such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium t-butoxide, sodium methylate, sodium ethylate or the like.
  • Optionally, the compound of the formula [I] thus obtained wherein X is hydrogen can be converted into a corresponding compound of the formula [I] wherein X is lower alkyl or halogen by a known method such as alkylation or halogenation.
  • The compound of formula [I] is present as E-isomer or Z-isomer, or a mixture thereof.
  • Regarding the compound of the formula [I], its E-isomer and Z-isomer can be represented by the following formulas:
    Figure imgb0004
     wherein X is as defined above, and W is
    Figure imgb0005
  • Further, the compounds of the formula [IV] are known as methylating agents.
  • The compound of the formula [I] thus obtained can be purified, if necessary, according to a conventional method, for example, column chromatography and can be used as an agricultural fungicide according to a known method.
  • As described above, according to the present invention, there is provided a novel process for producing methoxyiminoacetamide compouonds which are useful as agricultural fungicides and the process of the present invention is economical with minimum by-products.
  • Reference may be made to the parent of this application, EP-B-0 468 775 and to the co-pending divisonal application, EP-A-0 606 924 for information on procedural chemistry relevant to the present process.
  • The following Examples and Reference Examples further illustrate the present invention in detail but are not be construed to limit the scope thereof.
    • Example 1 Production of E-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide
  • To E-2-hydroxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide (10.00 g, 0.037 mole) were added acetone (200 ml), potassium carbonate (15.34 g, 0.111 moles) and.dimethylsulfate (9.33 g, 0.074 moles) and the mixture was stirred at room temperature for 9 hours. After completion of the reaction, the reaction mixture was filtered, washed with acetone and concentrated under reduced pressure. The oil thus obtained was dissolved in toluene (50 ml) and to this was added an aqueous 1N sodium hydroxide solution (50 ml), followed by stirring at room temperature for 30 minutes. The mixture was extracted with toluene, washed with water and concentrated, and then the resulting residue was recrystallized (methanol/water) to obtain E-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide (9.93 g, yield: 94.4%) as colorless crystals (melting point: 81.5-83°C).
  • 1HNMR (CDCl3) δ ppm: 2.87 (d, 3H, J=5.0Hz), 3.91 (s, 3H), 6.65 (br, s, 1H), 6.87-7.38 (m, 9H)
    • Example 2 Production of E-2-methoxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide
  • E-2-hydroxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide (1.00 g, 0.0035 mole) was dissolved in dried acetone (7 ml), and potassium carbonate (0.63 g, 0.0046 mole) and dimethylsulfate (0.53 g, 0.0042 mole) were added to the mixture, which was reacted at room temperature for 22 hours. After completion of the reaction, water was added to the reaction mixture, which was extracted twice with methylene chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (ethyl acetate/n-hexane) to obtain E-2-methoxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]-acetamide as colorless crystals (0.96 g, yield: 92.3%).
  • 1HNMR (CDCl3) δ ppm: 2.29 (s, 3H), 2.81 (d, 3H, J=4.9Hz), 3.89 (s, 3H), 6.71 (br, s, 1H), 6.82 (d, 1H, J=8.1Hz), 6.89-6.92 (m, 2H), 7.05-7.10 (m, 3H), 7.23-7.31 (m, 2H)
    • Reference Example 1 Production of E-2-hydroxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide
  • To crude E-α-hydroxyimino-2-phenoxyphenylacetic acid methyl ester (39.6 g, 0.0747 mole, purity: 51.2%) were added methanol (100 ml) and 40% aqueous solution of methylamine (15.45 g, 0.199 mole) and the mixture was stirred at room temperature for 15 hours. Then, 40% aqueous solution of methylamine (7.73 g, 0.0995 mole) was added to the mixture which was stirred in an oil bath at 70°C for 6 hours. After completion of the reaction, water (200 ml) and toluene (100 ml) were added to the reaction mixture, which was stirred with ice cooling for one hour. The precipitated crystals were filtered off and recrystallized (methanol/toluene) to obtain E-2-hydroxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide (12.31 g, yield: 60.1%) as colorless crystals (melting point: 183-184.5°C).
  • 1HNMR (d6-DMSO4) δ ppm: 2.65 (d, 3H, J=4.5Hz), 6.30-7.47 (m, 9H), 7.92 (q, 1H, J=4.5Hz)
    • Reference Example 2 Production of E-2-hydroxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide
  • E-α-hydroxyimino-2-(4-methylphenoxy)phenylacetic acid methyl ester (1.00 g, 0.0035 mole) was dissolved in methanol (7 ml) and 40% methylamine solution in methanol (0.54 g, 0.007 mole) was added to the mixture, which was refluxed for 70 minutes. A 40% methylamine solution in methanol (1.36 g, 0.0175 mole) was further added to the mixture, which was refluxed for 3 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to give E-2-hydroxyimino-N-methyl-2-[2-(4-methylphenoxy)phenyl]acetamide (1.00 g, yield: 100.0 %) as an amorphous.
  • 1HNMR (CDCl3) δ ppm: 2.31 (s, 3H), 2.86 (d, 3H, J=5.9Hz),6.60 (br, s, 1H), 6.84-7.36 (m, 8H), 7.93 (br, s, 1H).

Claims (7)

  1. A process for producing a compound of the formula [I]:
    Figure imgb0006
     wherein X is hydrogen, C1-C6 alkyl, C1-C6 alkoxy or halogen; and ~ is any configuration of E-isomer, Z-isomer or a mixture thereof, which comprises reacting a compound of the formula [V]:
    Figure imgb0007
     wherein X and ~ are as defined above and M is hydrogen or an alkali metal, with a compound of the formula [IV]:

            CH3-L     [IV]

    wherein L is halogen or -OSO2OCH3.
  2. A process according to claim 1, wherein the reaction of the compound [V] with the compound [IV] is conducted in a solvent in the presence of a base at -20 to 120°C for 15 minutes to 5 hours.
  3. A process as claimed in claim or claim 2, wherein is a C1-C4 alkyl.
  4. A process as claimed in claim 3, wherein X is methyl.
  5. A process as claimed in claim 1 or claim 2, wherein X is C1-C4 alkoxy.
  6. A process as claimed in claim 1 or claim 2, wherein X is hydrogen.
  7. A process for making a fungicidal composition wherein a compound of formula (I) is prepared by a process as claimed in any one of the preceding claims and thereafter the resulting compound is formulated into a fungicidal composition with one or more diluents, excipients or carriers.
EP94101360A 1990-07-26 1991-07-24 Process for producing methoxyminoacetamide compounds Expired - Lifetime EP0605392B1 (en)

Applications Claiming Priority (3)

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JP200696/90 1990-07-26
JP2200696A JPH0725727B2 (en) 1990-07-26 1990-07-26 Process for producing methoxyiminoacetamide compound
EP91306762A EP0468775B1 (en) 1990-07-26 1991-07-24 Process for producing methoxyiminoacetamide compounds and intermediates

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EP94101361A Expired - Lifetime EP0606924B1 (en) 1990-07-26 1991-07-24 Process for producing E-isomers of methoxyminoacetamide compounds
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US (1) US5183921A (en)
EP (3) EP0468775B1 (en)
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KR (1) KR100192200B1 (en)
AT (3) ATE115551T1 (en)
DE (3) DE69105850T2 (en)

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US5650539A (en) * 1990-07-26 1997-07-22 Shionogi & Co., Ltd. Process for producing alkoxyiminoacetamide compounds and intermediates
US5380913A (en) * 1990-07-26 1995-01-10 Shionogi & Co., Ltd. Process for producing methoxyiminoacetamide compounds and intermediates
DE4030038A1 (en) * 1990-09-22 1992-03-26 Basf Ag New 2-substd. phenyl-acetamide derivs. - useful as fungicides, insecticides, acaricides and nematocides
EP0741125A1 (en) 1992-11-02 1996-11-06 Shionogi Seiyaku Kabushiki Kaisha Benzyl compounds and process for producing same
DE4320499A1 (en) * 1993-05-14 1994-11-17 Bayer Ag Process for the preparation of 2-oximinoacetic acid derivatives
BR9405497A (en) * 1993-07-02 1999-05-25 Shionogi & Co Process for the production of alpha-alkoxyiminophenylacetonitrile derivatives
US5629442A (en) * 1993-07-02 1997-05-13 Shionogi & Co., Ltd. Process for producing α-hydroxyiminophenylacetonitriles
JP3220733B2 (en) * 1993-09-16 2001-10-22 塩野義製薬株式会社 Acetamidines, method for producing the same, and method for producing acetamides using the same
TW305836B (en) * 1994-05-20 1997-05-21 Shionogi & Co
DE4419587A1 (en) * 1994-06-03 1995-12-07 Bayer Ag Heterocyclic imino derivatives
EP0691332B1 (en) * 1994-07-06 1999-09-08 Basf Aktiengesellschaft Pyrazolyl derivatives, their preparation and their use as pesticides
DE19956920A1 (en) * 1999-11-26 2001-05-31 Bayer Ag Production of 2-(2-hydroxyphenyl)-2-alkoxyimino-N-methylacetamide compounds, useful as intermediates for fungicides, via new intermediates
JP5198877B2 (en) * 2006-01-31 2013-05-15 株式会社エーピーアイ コーポレーション Method for producing benzazepinones
CN102603563B (en) * 2012-01-16 2014-03-12 山东康乔生物科技有限公司 Preparation method of metominostrobin
CN108129349A (en) * 2017-12-19 2018-06-08 西安近代化学研究所 The synthetic method of one kind (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide

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IT1110460B (en) * 1977-03-02 1985-12-23 Ciba Geigy Ag PRODUCTS THAT PROMOTE THE GROWTH OF PLANTS AND PRODUCTS THAT PROTECT PLANTS BASED ON BODY ETHERS AND BODY ESTERS THEIR PREPARATION AND USE
US4490167A (en) * 1979-08-06 1984-12-25 Ciba-Geigy Corporation Oxime derivatives of diphenyl ethers and their use in herbicidal compositions
DE3623921A1 (en) * 1986-07-16 1988-01-21 Basf Ag OXIMETHER AND FUNGICIDES CONTAINING THEM
GB8617648D0 (en) * 1986-07-18 1986-08-28 Ici Plc Fungicides
ATE145891T1 (en) * 1989-05-17 1996-12-15 Shionogi & Co METHOD FOR PRODUCING ALKOXYIMINOACETAMIDE DERIVATIVES AND AN INTERMEDIATE PRODUCT THEREOF

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DE69105850D1 (en) 1995-01-26
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EP0605392A1 (en) 1994-07-06
DE69125629D1 (en) 1997-05-15
US5183921A (en) 1993-02-02
EP0468775B1 (en) 1994-12-14
KR100192200B1 (en) 1999-06-15
EP0468775A1 (en) 1992-01-29
JPH0489464A (en) 1992-03-23
DE69105850T2 (en) 1995-04-27
ATE151411T1 (en) 1997-04-15
ATE115551T1 (en) 1994-12-15
DE69126446T2 (en) 1997-11-27
ATE154002T1 (en) 1997-06-15
EP0606924B1 (en) 1997-06-04
JPH0725727B2 (en) 1995-03-22
DE69126446D1 (en) 1997-07-10

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